Process for the chlorination of hydrocarbons



. Patented-July 13,4926.

"UNITED STA res;

PATEN r or-rice.

.EOLZVERKOHLUNGSJNDUSTRIE AKTIEN-GESEIQLSCHAFT, OI CONS'IAHCE, BA-

pnm, ama-ANY, A conronarron or (murmur; I

4 rnooass ron rnn cnnonmarron ornxnnooan'nons.

1T0 Drawing. Application filed une 4, 1924, Serial 30,217,890, and in German November 15, 1923.

The invention relates to the chlorination of hydrocarbons such as for instance methane and its. homologues, acetylene, benzene, and so on, by the action of chlorine at a high temperatures in the presence or in the absence of catalysts.

- It has been possible according to the inventi'on to convert the chlorine to an exceptionally complete: extent into chlorinetion products, this eflect being obtained byaddingoxygen or gas mixtures containing oxygen, for instance air, to the mixture of hydrocarbon and chlorine.

The quantity of oxygen to be used depends on the products aimed at and the method or working. The supply of oxygen 'may .for instance be in theoretical quantlties, that is to say, in quantities which are required for the oxidation of the hydrogen split 03 from the hydrocarbon, water being 4 formed at the same time. In the conversion of methane into mono-chloro-methanefor instance the amount of oxygen to be added will-be calculated according to the following reaction equation:

Foricarrying out the process in practice, it has in general been. found of advantage to add a definite excess of oxygen .over and above the theoretical quantity. By observing suitablecreaction conditions, such as for instance the avoidanceof overheating and the correct regulationof'the. velocity of flow of the gases the work can be carried out with considerable excesses of oxygen, for example up to 109% and more, without detrimental e ectS, such as for examplean undesired oxidation of considerable quantities of the hyw drocarbon, for instance withthe formationof carbon dioxide. The process may be'carried out in the absence of catalysts,-preferably however with catalysts having the capacity to assist the desired chlorination of M the-hydrocarbon, but 'notian undesired oxidatib'n of the same. The 'pres'ence*ofcatalysts makes it for instance possible to carry out the process at low reaction temperatures.

Ascatal sts use may be made for instance of metal 'aloids, such as cupric chloride; iron chloride, thellic chloride, also the chlo l' rides of the alkaline earths and of the rare earths, carbon (animal carbon, active carhon) and other chlorine carriers.-

The most suitable working temperatures are from about 300 C. to about 650 0., more particularly from about 400 C. to

about '550 C. Excessive heating which" Imght cause undesired oxidation of the hydrocarbon to be chlorinated should be.

avoided.

I The chlorination of hydrocarbons by the" action of chlorine under conditions, in which the hydrogen'split oil fromthe hydrocarbon 1s oxldized to water, has the particular advantage that hereby Water v'apouris .pro-

,duced, which represents a valuable diluent, -wh1ch is able to prevent explosions or other undesired subsidiary reactions. In spite of this positive formation of water va our, ad-

ditional quantities of. diluents, suc as for example superheated steam, hydrochloric Y acid, and the like may be added, but this is not necessary if the present process is car- I ried outcorrectly, as it-is possible to producewater vapour in quantities which arej air. The invention offers the further ad- 'capable of preventing explosions and. the I like with certainty b umeans ofthe added oxygen, for instance y the introduction of vantage that by oxidation of the hydrogen split off from the hydrocarbon, the heat thereby produced may be utilized directly forcarrying out-the chlorination process. The invention will be illustrated in more detail by a few examples, which show the alternativeworking conditions which can be employed with respect to the proportions,

catalysts, temperatures, velocity of .flow',"

diluents and so on.

Emample 1.-I nto nal diameter 600 contains. chamotte soakedwith cupic chloatube of 30 mm. interride, there are introduced inthe course of an hour 25 litres of methane, 6' litres of chlorine and: 31klitres of air; The tempera-j ture is keptat 4b'O' C.-500 C. 93% of the chlorine used is converted into chlorinationproduc sf, Ze 2.-In,t o the same tube there are E mi int'rodfi'ced in the fc'ourse of'an hour 13 litres mm. heatable length, which 4 of methane,'6 litres of chlorine and 22 litres methane. V

Example 3.-Into a tube of '30 mm. in

ternal diameter, which is charged to a length of 60 cm. with chamotte grains and in the remaining art with grains soaked in cu'pric chloride, ti ereis introduced in the course 28 litres thereof per hour. The first part of of an hour a mixture of 25 litres methane and 6 litres chlorine in such a manner'that the gas mixture has first to pass through the part of the tube charged with non-prepared ch-amotte grains. At the'point of contact of the non-impre ated and impregnated chamotte grains air-is introduced, that is to say the tube is kept at a' temperature of for example 360 (1., the second part at about 450 C500 C. 95% of the introduced chlorine is obtained in the form of chlorination prod nets of the methane.

Example 4.%Into the tube described in Example 3, there are introduced in the course of an hour 12' litres of methane, 6 litres of chlorine and about 25 litres of steam, at a temperature somewhat belew 400 C. in the first half of the tube. In the second half of the tube after the supply of 25 litres of air, the temperature is kept between 450 C: and 500 C. 88% of the introduced chlorine is converted into chlorination products.

Many hydrocarbons, for example natural ases, contain oxygen, the presence of which is to be attributedjto the gas being rendered impure by air. It has however not been known that such natural gases containing 0 gen' were chlorinated by the action of ch orine at higher temperatures On the other hand it is known that the gases to be chlorinated are often subjected to a preliminary purification, for instance by passing over glowing palladium, platinum, or the like (of. Austrian Patent 58,273). In a preliminary treatment of this kind, any'oxygen that was present would naturally be removed at the same time.

As it was to be feared that with the presence of considerable quantities of oxygen,

undesired secondary reactions, such as for instance oxidation of the hydrocarbom-deposition of carbon black, and in some cases even explosions would take place, it can be understood vthat hitherto a chlorination in the presence of considerable quantities of oxygen as been abstained from. The knowled e that it ispossible easily to carry out t e chlorination process in the presence of considerable quantities of oxygen, atthe same' time obtaining important advantages, is a surprising result of technical importance.

What I claim is:- v r v 1. Process for the chlorination of saturated hydrwarbons eonsisting in causing the '7 temperatures of 300 to 650 C. in the pressuch that undesirable oxidation of the hydrocarbon is avoided.

2. Process for the chlorination of saturated hydrocarbens consisting in causing the said hydrocarbons to react with chlorine at temperatures of 300 to 650 C. in the presence of suflicientoxygen to convert the hydrogen split off from the hydrocarbon into water, the quantity of oxygen employed and the velocity of the gases being such that undesirable oxidation ofthe hydrocarbon is avoided. V

3. Process for: the chlorination of saturated hydrocarbons consisting in causing the said hydrocarbons to react with chlorine at temperatures of 300 C. te 650 C. in the presence of oxygen and with the addition of diluting means, the quantity of oxygen employed and the velocity of the gases being such that undesirable oxidation of the bye drocarbon is avoided.

4. Process as claimed in claim 3 in which the diluting means employed is superheated;

' quantity of oxygen employed and the velocity of the gases bein such that undesirable oxidation of the hy rocarbon is avoided.

6. Process as claimed in claim'5 in which the reaction is effected in the presence of a metallic chloride as catalyst. V r

7 Process as claimed in claim 5 in which the reaction is efi'ected in the presence of copper chloride as "catalyst. V

8. Process for the chlorination of methane consisting in causinl the said gas to react with chlorine at temperatures of 300 to 650 C. in the presence of oxygen, the quantity of oxygen employed and the velocity of the gases bein suchthat undesirable oxida tion of the hy rocarbon is avoided.

9. Process fr the chlorination of methane consisting in causing the said gas to react with chlorine at temperatures of 300 to 650 C. in the presence of air and in the resence of a catalyst capable 'of aiding chlorination, the quantity of air employed and the velocity of the gases being such that undesirable oxidation of the i methane is avoided.

10. Process for the chlorination of saturated hydrocarbons consisting in causing the said hydrocarbons to react with chlorine at temperatures of 300 to 650 C. in the presence of oxygen, in the presence or a catalyst capable of aiding chlorination and also in the presence of diluting means, the quantity temperatures of 300 of oxygen employed and the velocity. of the gases bein such that undesirable oxidation I of the hy rocarbon is avoided.

11. Process for the chlorination of satu-' rated hydrocarbons consisting in. causing the said hydrocarbons to react with chlorine at to 650 C. in the pres-.

ence of oxygen and diluting means, the quantity of oxygen; employed and the velocity of the gases being such that undesirable oxidation of the hydrocarbon is avoided.

12. Process as claimed in claim 8 in which the reaction is effected in the presence of diluting means.

In testimony whereofwe aflix oursignatures. v

ERICH KRAUSE.

. KQLOMAN ROKA. i 

